Styrenic Block Copolymers in

Medical Applications

Presented by Julie Li

InterPlas Thailand 2013

June 20, 2013, Bangkok

Outline

Introduction to Kraton Polymers, Inc.

What are KratonTM Polymers?

Kraton Enhanced Rubber Segment (ERS) Grades and Applications

Kraton Adhesive Compounds for Protective Film Applications

CariflexTM Polyisoprene Rubber and Applications

Summary

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Kraton Polymers, Inc. at a Glance

Specialty polymer company with 2012 revenues of $1.4B (KRA);

Inventor and a leading producer of styrenic block copolymers (SBCs);

Manufacturer of highly engineered polymer solutions with product breadth,

service, and technical support second to none;

Designer of customized solutions on a molecular level to meet specific

performance needs;

Serves a highly diverse set of end-use applications in addition to dedicated

emerging businesses;

Seller of over 800 products to approximately 800 customers in 60 countries;

Holder of approximately 1,400 patents; issued or pending;

Employer of approximately 940 people in 9 locations in all major regions of the

world.

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Kraton Polymers Can Support Your Global Demand

Belpre, Ohio U.S. Manufacturing Facility

Corporate Headquarters

Houston, Texas U.S.

Innovation Center

Paulinia, Brazil

Manufacturing Facility Innovation Center

Mont St. Guibert, Belgium Technical Service Office

Wesseling, Germany Manufacturing Facility

Tsukuba, Japan Innovation Center Kashima, Japan Manufacturing Facility

Berre, France Manufacturing

Facility

Shanghai, China

Amsterdam,

Regional Headquarters

Innovation Center

Netherlands

Mailiao, Taiwan Future Asia HSBC Plant

Regional Headquarters

Innovation Center

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50 Years of Innovation and Growth

Nexar™ Polymers

Cariflex™ Polyisoprene Products

What are KratonTM

Polymers?

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Styrenic Block Copolymer (SBC) SEBS, SEPS, SBS, SIS, SIBS, …

1. Precise control of block size and formation;

2. Precise control of molecular weight;

3. Narrow molecular weight distribution;

4. Precise control of midblock structure;

5. High hydrogenation ratio.

Features of Anionic Polymerization

PS PS Rubber

SBS

SEBS

USBC Kraton D polymers

HSBC Kraton G polymers

+ H2

What are Kraton™ Polymers?

What are Kraton™ Polymers?

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Styrenic Block Copolymer (SBC) is a thermoplastic elastomer

Morphology of

Kraton Polymer

TEM micrograph（S/B=20/80%)

~200 Å

Domain Size

Rubber

Mid Block

Polystyrene

End Block Hard Tg = 100℃

Incompatible with soft block Strength enhancer

Physical crosslinks at room temperature

Soft & Flexible Low Tg

SBS = -90℃, SIS = -60℃, SEBS = -55℃

Oil-able, Strength Hydrophobic

Stable

Two incompatible

phase structures:

vulcanization NOT

Required

Product Families

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Enhanced Rubber Segment ERS and Applications

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Kraton™ ERS grade - Enhanced Rubber Segment

Key Benefits:

FDA and USP VI approved for food / medical applications;

Add materials at the machine, no need to pre-compound;

High stiffness and impact allows for reduced wall thickness;

Use in injection molding, sheet extrusion and blow molding.

Transparent PP impact modifications for packaging

PVC alternative for e.g. medical bags & tubing

Clarity and flexibility for films and food wrap

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ERS for Transparent PP Modification

Features/Benefits

Kraton™ G polymers show good weather and aging performance;

ERS grades show better compatibility with PP than conventional SEBS grades;

Clear blends with clarified PP;

G1643 shows lowest viscosity for easy dispersion: Injection molding;

G1645 is the softest SEBS grade available, higher viscosity: Injection molding possible, but more suited for film extrusion (Cast/Blown);

G1643 and G1645 pass ISO 10993 testing (USP Class VI);

G1643 and G1645 are available in dense pellets for easy extruder handling and blending with PP pellets: no need for separate compounding step;

Articles of PP and G1643 (or G1645) can be steam, EO, EB, or gamma sterilized.

S EB S

G1643

G1645

Typical Properties

G1643 G1645 Polymer SEBS SEBS Rel. MW 1.1 1.4 PSC % 20 13 Shore A 52 34 Rubber Tg, oC -35 -35 MFR (200C,5kg) 18 3.5 MFR (230/5kg) >70 7 Physical Form Pellet Pellet

Enhanced Rubber Segment

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ERS: Finer Dispersion in PP Matrix

Transmission Electron Microscopy Pictures

G1642/PP: 50/50 G1650/PP: 50/50

Standard SEBS: Coarse network ERS Improved compatibility Finer network

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ERS for PP Modification

PP Homopolymer modified with G1643

0

100

200

300

400

0 5 10 15 20

%wt G1643

Inst

rum

ente

d

Impact

@23C

(in-lb

s)

55

60

65

70

Haze (

%)

Impact Haze

In PP homopolymer the haze reduces and the impact properties improve with

increasing amount of G1643;

Note! Increasing amount of G1643 reduces the flexural modulus and heat deflection

temperature. 14

Improved clarity of PP/G1643 Blends

Haze = 8.0% Haze = 69%

(100% PP) (60% G1643) (20% G1643) (40% G1643)

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Kraton™ ERS modified PP vs. PVC

Kraton ERS polymers are the best modifiers of polyolefins as an alternative for

PVC in various applications

ERS modified PP Soft PVC

Relative Gravity ~0.9 >1.2

Low MW Plasticizer Not Necessary >30%

Plasticizer Migration N Y

Service Temp. Range -20~70oC, less hardness change in

work temperature range

Hardness highly affected by

temperature

Thermal Stability Minimal degradation below 250oC Start degrading at 130oC

Durability Excellent UV, Ozone & chemical

resistance

Poor heat & UV resistance

Environmental Impact Minimal hazardous chemicals

generated during thermo

processing or combustion

Hazardous chemicals e.g. HCL,

Dioxins etc. generated at high

temperature

Recyclability Easy recyclable due to excellent

compatibility with polyolefin

Hard to recycle when blend with

other polymers

Wide formulating latitude;

Wide working temp. range;

Non-hazardous;

Clear.

Recyclable;

Safe;

Overmolding to PO;

Adhesion to PO layer.

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Kraton™ ERS modified PP in Medical – IV Bag

Technology

Multi-layered co-extrusion film, cast & blown

Example of IV bag made through co-extrusion film

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Outer layer (printing layer) • Main material ： PP ( + ERS ) • Requirements ： heat stability, scratch resistance, printability

Mid-layer • Main material ： PP ( + ERS) • Requirements ： flexibility, clarity

Inner layer (sealing layer) • Main material ： PP ( + ERS) • Requirements ： low seal initiation temp, high seal strength

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Kraton™ ERS modified PP in Medical – IV Bag

Market Trend

Switching from glass bottle to plastic bottle and from PVC to

polyolefin based.

Requirements

Transparency;

Resistance to sterilization（Steam: 121℃ 20～30min;

Flexibility and low temp impact;

Resistance to different fluids;

Heat sealability（150℃～170℃ 1～2 sec）

Technology

Multi-layered co-extrusion film, cast & blown.

Opportunity

PP/ERS blends;

Starting point

Blend with G1645 or G1643.

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Kraton™ ERS modified PP in Medical – Tubing

Kraton G1645 polymer successfully passes all ISO 10993

biological toxicity testing for use in medical

applications and is USP VI approved;

Plasticizer-free G1645-RCPP combinations provide a

wide operating window for flexible medical tubes and

are potentially able to replace soft PVC when

considering:

Extrusion technology (mono- versus multi-layer);

Type of PP;

G1645-PP ratio.

Depending on the type of PP the same sterilization

techniques are applicable to G1645 based blends as to

PVC;

Surface tackiness can be resolved with the addition of

slip agent;

Laser welding recommended for medical device

assembly with PP-based parts. Kraton-based

formulations are not recommended for joining to

plasticized PVC.

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Kraton™ ERS Modified PP in Medical – More Examples

Features

Clean

Clear

Impact resistance at room & low temperature

Mechanical strength

Low extractable

Sterilizable

Opportunities

Syringe devices

IV Bottles

Drug bottle/containers

Medical device containers

(Kraton SBC polymer based elastomeric compounds also applicable for flexible

medical parts, e.g. syringe gasket)

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Kraton™ ERS modified PP in

Transparent Consumer Goods Applications

Opportunities

Food container

Baby bottle

Water bottle

Containers

Ice-trays

Home appliance parts

PP modification with innovative ERS Kraton polymers result in a

good balance of transparency, stiffness, and impact strength

Features

Transparency

Impact resistance

Mechanical Strength

Wide service temperature range

Processability

Compatibility with other

polymers

Low relative gravity

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Transparent PP to Replace BPA Based PC

Kraton Polymers’ approach:

Replace BPA containing PC with Random Copolymer PP (RCPP). Nucleated RC PP is widely accepted in food industry, is quite transparent, rigid and resistant to sterilization temperatures. Transparent RC PP however lacks impact resistance at room temperature and fridge temperatures.

Kraton Polymers’ solution:

Use 7-10% of KratonTM G1643 in nucleated transparent RCPP. Most advanced nucleated RCPP are required to get maximum transparency.

Kraton G offers:

Easy to inject, BPA-free solution;

Improved PP impact at room and fridge T;

Effectiveness not impacted by sterilization;

Cost reduction versus PC.

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Due to health concerns regarding BPA based PC Kraton investigated alternatives.

Impact Modification for Transparent PP Containers

Problem:

Totes and bins made of transparent PP tend to crack during shipment to retailers and during early customer use.

Approach:

Many customers assume that metallocene modifiers would be the cheapest solution. But metallocene level tends to be 20% while KratonTM G at 3%-10% loading levels is OK.

Solution:

Use of Kraton G as a modifier in PP storage bins resulted in cost reduction and performance gains for customers.

Kraton G offers:

Improved impact;

Improved transparency;

Cost reduction via lower concentration levels.

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Kraton™ ERS in Films and Food Wrap Applications

Features

Kraton polymers can help polyolefins to meet

higher performance in films:

Maintain clarity, low haze;

Increase toughness;

Help to achieve Low modulus /flexibility;

Boost impact and puncture resistance;

Increase MD tear strength;

Tough tie layer in co-ex films;

Lower initial seal temperature.

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Opportunity

PP/ERS blends;

Starting point:

PE films: G1657, G1645, G1643

PP films: G1645, G1643, G1657

Enhanced Rubber Segment ERS and Applications -

Summary

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Enhanced Rubber segment Grades have a better compatibility with PP than the conventional SEBS grades;

FDA and USP VI approved for food / medical applications;

High stiffness and impact allows for reduced wall thickness;

Can be added at the machine, no need to pre-compound;

Can be used in injection molding, sheet extrusion and blow molding.

KratonTM Adhesive Compounds for Protective Film Applications

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Example Applications

LCD panel;

Prism film;

White goods;

Window/mirror;

New auto protection.

Key features and benefits

Lower system costs;

Superior Protection;

High Flexibility and Customizable Peel Strength;

Haze and residue-free;

VOC-free.

Kraton™ Polymers in Protective Film Applications

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Kraton melt extrudable products allow one step co-extrusion to save

cost and provide superior performance for metal and plastic surfaces

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Kraton™ Co-extrusion Technology - Values

Lower system costs One-step co-extrusion process using pelletized compounds;

Eliminates multi-step coating and drying steps required of conventional, solvent cast films;

Purchase/production of backing film (as used in the coating process) is not required;

Does not require expensive ovens.

Features and benefits Sustains tack on curved and textured surfaces;

Tailored peel strength (~ 0.9-6.5 N/25mm);

Adheres to a wide variety of substrates chemistries and topographies.

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Kraton™ Adhesive Compounds (5-15 µm)

PE/PP Backing (40-50 µm)

PE/PP + Antiblock (5-10 µm)

A typical PF film is 3 layers (A+B+C) 50 – 70µm thick;

A – adhesive layer usually 5 – 10 µm thick;

B – core layer (LDPE/PP) 40 – 50 µm thick;

C – outside layer (PP, HDPE or LDPE/HDPE blend 5 – 10 µm thick; This layer can also contain anti – block. The use of HDPE and anti-block in this layer will aid in the unwinding of the finished roll.

Rheology match is needed for each individual layer of the film!!

Protective Films: Film Structure Recommendation

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Kraton™ Protective Film Compounds: Overview

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Kraton™ Adhesive Compounds for

Protective Film Applications - Summary

Kraton adhesive compounds for co-extrusion consist of rubbery, free-flowing pellets;

Adhesives can be made having a broad range of tack and adhesion, adhesion to both polar & non-polar surfaces;

One-step co-extrusion process, lowers overall system costs;

Compatible on polyolefin backings (PE or PP) to make removable protective films;

Kraton adhesive compounds for co-extrusion provide the following, as a finished protective film:

Superior Protection

High Flexibility and Customizable Peel Strength

Clean Film

CariflexTM Polyisoprene Rubber and Applications

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What is Cariflex™ Polyisoprene (IR)?

Polyisoprene elastomers are:

Synthetic;

Predominantly stereoregular;

Resembling natural rubber in molecular structure and properties.

There are two major synthetic polyisoprene types with high cis-1,4 content:

Ziegler-Natta (high cis) IR, polymerized in the presence of a titanium/aluminum catalyst;

Anionic IR, polymerized with an alkyl-lithium initiator.

Different polyisoprene production processes give different products

Cariflex IR Ziegler-Natta IR Natural Rubber

Cariflex™ IR & IR Latex Applications

Electronic coatings; Printing inks; Glues

Marine coatings

Medical stoppers and other medical rubber pieces

Catheters (heart, urinary)

Condoms

Surgical gloves

Physiotherapy bands

Medical bandages

Cold seal adhesives for food & medical packaging

IR solid material Pure Transparent Elastic Soft Strong

Stoppers for IV bags

Dental dams

Transparent shoe soles

Needle shields

Cariflex IR IR Latex material

Potential Applications for

Transparent Vulcanized Compounds by Cariflex™ IR

Cariflex IR

KICT TR series

Formulating

technology

Transparent shoe soles

Transparent key board

Cover

Rubber seal for Y-injection site

Baby nipple

Rubber tubing for

medical pump

Compression-molded tube

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Summary

KratonTM polymers offer a wide range of flexibility in polymer design and

formulations that are suitable to diverse applications;

Kraton ERS grades have a better compatibility with PP than the conventional SEBS

grades, offering a wide range of applications including PVC replacement:

FDA and USP VI approved for food / medical applications;

High stiffness and impact allows for reduced wall thickness;

Can be added at the machine, no need to pre-compound;

Can be used in injection molding, sheet extrusion and blow molding.

Kraton adhesive compounds for protective film applications allow one step co-

extrusion to save cost and provide superior performance for metal and plastic

surfaces;

CariflexTM IR is an unique polyisoprene rubber giving many advantageous

performance over the conventional rubber systems in PURE - SOFT- STRONG

applications.

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We believe the information set forth above to be true and accurate, but any findings, recommendations or suggestions that may be made in the foregoing text are without any warranty or guarantee whatsoever, and shall establish no legal duty or responsibility on the part of the authors or any Kraton Polymers entity. Furthermore, nothing set forth above shall be construed as a recommendation to use any product in any specific application or in conflict with any existing patent rights. All Kraton Polymers entities expressly disclaim any and all liability for any damages or injuries arising out of any activities relating in any way to this publication or the information set forth herein. ©2013 Kraton Performance Polymers, Inc. All rights reserved.

Publication Disclaimer:

Kraton, the Kraton logo and design, the Cariflex logo, Cariflex, Nexar and the Giving Innovators Their Edge tagline and in some cases, their expression in other languages are trademarks of Kraton Performance Polymers, Inc. and are registered in many countries throughout the world.